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1.
The long-chain alkyl derivatives of a nucleoside analogue-acyclovir were prepared in the paper. One is stearyl-glycero-succinyl-acyclovir (SGSA) with a single 18-carbon length (C18) alkyl chain. Another is dioctadecyl-aspartate-succinyl-acyclovir (DASA) with double C18 alkyl chains. They were prepared by the esterification of succinyl-acyclovir with the lipids, and sodium salts of them were also prepared. Guanine moieties and alkyl moieties bring the derivatives intermolecular hydrogen bonding and hydrophobic interaction in water separately. The forces are influenced by the number of alkyl chains and the charged state, and determine the solubility and the self-assembly behavior of the derivatives. The double alkyl-chain derivatives (DASA and DASA-Na) formed rigid Langmuir monolayers on air/water surface, while the single alkyl chain derivatives (SGSA and SGSA-Na) did not. However, cholesterol (Chol) could assist SGSA to form rigid monolayers through inserting into the alkyl chains of SGSA to mimic the second alkyl chain. SGSA self-aggregates in water were prepared by the injection method with tetrahydrofuran as solvent. Cuboid-like shape and nanoscale size demonstrated that SGSA self-aggregates were self-assembled nanoparticles. Shape, particle size, zeta potential and phase transition of the nanoparticles were characterized. And they showed an average size of 83.2 nm, a negative surface charge of -31.3-mV zeta potential and a gel-liquid crystalline phase transition of 50.38 degrees C. The formation mechanism of self-assembled nanoparticles was analyzed. Hydrophobic interaction of alkyl chains improves SGSA molecules to form bilayers, and then cuboid-like nanoparticles were obtained by layer-by-layer aggregation based on inter-bilayers hydrogen bonding. However, the charged guanine moieties make SGSA-Na lose the function of hydrogen bonding so that SGSA-Na only forms vesicles in water based on hydrophobic interaction. Strong hydrophobicity and wide-open rigid double alkyl chains of DASA and DASA-Na restrict self-assembly in water media, and no homogeneous suspensions were obtained. Therefore, the molecular self-assembly behavior of the long-chain alkyl derivatives of nucleoside analogues on water surface or in water media is determined by the number of alkyl chains and the charged state. 相似文献
2.
The melting of alkyl chains in the saturated fatty acid zinc soaps of different chain lengths, Zn(C(n)H(2n+1)COO)(2); n = 11, 13, 15, and 17, have been investigated by powder X-ray diffraction, differential scanning calorimetry, and vibrational spectroscopy. These compounds have a layer structure with the alkyl chains arranged as tilted bilayers and with all methylene chains adopting a planar, all-trans conformation at room temperature. The saturated fatty acid zinc soaps exhibit a single reversible melting transition with the associated enthalpy change varying linearly with alkyl chain length, but surprisingly, the melting temperature remaining constant. Melting is associated with changes in the conformation of the alkyl chains and in the nature of coordination of the fatty acid to zinc. By monitoring features in the infrared spectra that are characteristic of the global conformation of the alkyl chains, a quantitative relation between conformational disorder and melting is established. It is found that, irrespective of the alkyl chain length, melting occurs when 30% of the chains in the soap are disordered. These results highlight the universal nature of the melting of saturated fatty acid zinc soaps and provide a simple explanation for the observed phenomena. 相似文献
3.
利用核磁共振化学位移变化, 自旋-自旋弛豫和2D NOESY(two-dimensional nuclear Overhauser enhancement spectroscopy)研究了一系列新合成的双取代烷基苯磺酸盐的胶束化. 结果表明, 邻位取代的是正烷烃链, 间位取代的是支烷烃链. 而且, 邻位取代的烷烃链越长, 参与形成胶束疏水核表面层的亚甲基个数越多. 因此, 每个分子在饱和吸附的油水界面上的面积越大. 间位取代的分支链在胶束疏水核中堆积得没有邻位取代的正烷烃链紧密. 分支链越短, 堆积得越不紧密. 描述了胶束中分子的相对排列. 相似文献
4.
以三羟甲基丙烷(TMP)为核,二羟甲基丙酸(DMPA)为支化单体,通过熔融缩聚法合成了第3代端羟基脂肪族超支化聚酯,并用十八酸对其进行端基改性,采用广角X射线衍射(WAXD)、示差扫描量热分析(DSC)及红外光谱(FTIR)研究了不同端基改性程度的超支化聚酯的结晶熔融行为及端烷烃链的构象和堆积结构随温度的变化,采用旋转流变仪研究了端烷烃链对脂肪族超支化聚酯熔体动态黏弹行为的影响.结果表明,这类改性超支化聚酯的结晶归因于长链端烷烃的有序排列,改性程度越高,衍射峰强度越大.受限结晶的端烷烃链在升温后并不能完全转变为无序的结构状态,改性超支化聚酯在"熔点"以上仍有部分有序结构存在.超支化聚酯的线性黏弹区随着端基改性程度的增大而逐渐变短,超支化聚酯的弹性逐渐增大,剪切变稀越明显.动态流变测试中所出现的现象与改性超支化聚酯中端烷烃链的受限密切相关. 相似文献
5.
Novel amphiphilic block molecules consisting of a rigid 2‐phenylthiophene or 5‐phenylbithienyl core, with a polar glycerol group attached to the phenyl ring and one or two alkyl chains attached to the thiophene ring on the other side, have been synthesised by using Ni(0) and Pd(0) catalyzed coupling reactions as key steps. The thermotropic and solvent‐induced liquid crystalline behaviour of these compounds was investigated by polarising optical microscopy and X‐ray diffraction. The influence of the length, number and position of the alkyl chains, and the length of the rigid core, on their mesophase behaviour was investigated. Compounds with one alkyl chain in the terminal 5‐position on the thiophene ring form only smectic A phases, compounds with two adjacent alkyl chains attached in the 4‐ and 5‐positions of the thiophene ring exhibit thermotropic columnar mesophases, and those with two long alkyl chains attached to the 3‐ and 5‐positions form columnar LC phases only in the presence of water. Another compound containing the longer 5‐phenylbithienyl core unit and two alkyl chains attached in lateral positions to each of the thiophene rings is not mesogenic. 相似文献
6.
合成了一系列烷基取代的间苯三酚衍生物,并在大气条件下用扫描隧道显微镜研究了它们在高定向裂解石墨表面的吸附和组装行为.实验结果表明,这些自组装分子具有条状结构特征.在链长较短的分子图像中,两条平行的烷氧基链肩并肩地排列在苯环的一侧,另一条烷氧基链则排列在苯环的另一侧,链与链之间彼此相互交错排列形成均一的烷基条带.当链长增加时,这种高稳定性和密排结构遭到破坏,出现单个分子和分子对共存的组装结构.这是由于烷基链与烷基链之间以及烷基链与基底之间的作用力共同决定的.通过调控分子烷基链的长度可以得到不同的表面二维纳米结构. 相似文献
7.
Jadwiga Szyd owska Adam Kr wczy ski Urszula Pietrasik Agnieszka Rogowska 《Liquid crystals》2005,32(5):651-658
Mesogenic tetradentate cis-enaminoketone Ni(II), Cu(II) and VO(II) complexes with rod-like and disc-like molecular shapes were synthesized. In these compounds some of the alkyl chains were perfluorinated. Replacing the alkyl chains by fluorinated chains stabilizes the columnar hexagonal Colh phase whereas lamellar phases are destroyed. 相似文献
8.
Penfold J Staples E Tucker I Thomas RK Woodling R Dong CC 《Journal of colloid and interface science》2003,262(1):235-242
The structure of mixed nonionic surfactant monolayers of monodecyl hexaethylene glycol (C10E6) and monotetradecyl hexaethylene glycol (C14E6) adsorbed at the air-water interface has been determined by specular neutron reflectivity. Using partial isotopic labeling (deuterium for hydrogen) of the alkyl and ethylene oxide chains of each surfactant, the distribution and relative positions of the chains at the interface have been obtained. The packing of the two different alkyl chain lengths results in structural changes compared to the pure surfactant monolayers. This results in changes in the relative positions of the alkyl chains and of the ethylene oxide chains at the interface. The role of the alkyl chain length is contrasted with that of the ethylene oxide chain length, determined from results reported previously on the nonionic surfactant mixture of monododecyl triethylene glycol (C12E3) and monododecyl octaethylene glycol (C12E8). 相似文献
9.
Egermayer M Karlberg M Piculell L 《Langmuir : the ACS journal of surfaces and colloids》2004,20(6):2208-2214
Previous work has shown that amylose (AM) can cross-link hydrophobically modified polymers by inclusion complexation, whereby thermoreversible cold-setting gels are formed. Here we investigate the complexation of AM with different samples of hydrophobically modified ethyl(hydroxyethyl) cellulose (HMEHEC), distinguished by differences in the architecture of the hydrophobes (the hydrophobic side chains). All hydrophobes, except one, were based on linear alkyl chains, but with varying chain lengths (C12-C14). In addition, some samples contained short hydrophilic "spacers", consisting of 2-5 ethylene oxide units, between the alkyl chains and the EHEC backbone. Gels of varying strength were obtained for the different AM/HMEHEC samples. The alkyl chain length seemed to be the major factor affecting the gel strength, with longer alkyl chains giving stronger gels. For similar alkyl chain lengths, stronger gels were obtained when a spacer was present. Addition of AM caused a small increase of the cloud points of HMEHECs with C14 hydrophobes in water. Time-dependent effects and effects of the sample preparation procedure were also investigated. The reversibility of the gelation with respect to shear was confirmed. A gel destroyed by added surfactant was shown to reform on removal of the surfactant by dialysis. 相似文献
10.
Dae-Shik Seo 《Liquid crystals》2013,40(11):1621-1624
A high pretilt angle for the nematic liquid crystal, 4-n-pentyl-4'-cyanobiphenyl (5CB), was observed on rubbed polythiophene (PTP) surfaces having alkyl chains with more than ten carbon atoms. We consider that this is due to a surface-excluded volume effect caused by the long alkyl chains between the LC molecules and the PTP surfaces. The polar anchoring strength in 5CB on rubbed PTP surfaces with long alkyl chains has also been successfully evaluated. The extrapolation length de of 5CB increases with increasing alkyl chain lengths above the seven carbons of alkyl chain R7; that is, it may be attributed to the high pretilt angle. An extrapolation length of 5 nm is observed in 5CB for the seven carbons alkyl chain R7 on the PTP surface; this indicates high anchoring strength. 相似文献
11.
Yano M Taketsugu T Hori K Okamoto H Takenaka S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(16):3991-3999
The series of alkyl 4-[2-(perfluorooctyl)ethoxy]benzoates (F8-n) shows a systematic change of crystal structures depending on the length of the alkyl chain: separate packing of perfluorooctyl (Rf) and alkyl (Rh) chains from each other for shorter (n=2) and longer (n=11) members, alternate packing of Rf and Rh chains for middle (n=6,7) members, and an intermediate type of packing for n=4. Semiempirical MO calculations show slightly repulsive interactions between the Rf chains, and attractive ones between Rf and Rh chains and between Rh and the core of a molecular pair. It is concluded that fluorination determines the molecular shape of the crystal structures by making the chain rigid. It is confirmed that the interactions between Rf chains are small compared with those between other moieties and that they are forced to aggregate owing to the exclusion from other moieties. Thus, the effect is dependent on the geometries and intermolecular interactions of the other moieties. 相似文献
12.
合成了3种含有不同长度烷基链的苯并菲盘状液晶化合物; 通过1H NMR 和 MALDI-TOF MS对其结构进行了表征; 利用差示扫描量热法(DSC)、热台偏光显微镜(POM)和小角X射线散射实验(SAXS)对3种液晶化合物的自组装行为进行了研究. 结果表明, 烷基链的长度对苯并菲盘状液晶化合物自组装结构的影响显著. 柔性链为辛基的苯并菲盘状液晶化合物自组装成六方柱状液晶相; 柔性链为十二烷基的化合物自组装成倾斜柱状液晶相; 而柔性链为十六烷基的化合物则未形成液晶相. 相似文献
13.
The photodimerization of a cinnamoyl moiety derivative in dilute solution based on the intramolecular chain interaction of gemini surfactant 总被引:1,自引:0,他引:1
A Gemini surfactant, sodium N, N'-di(4-n-butyloxy cinnamoly)-L-cystine, containing a cinnamoyl moiety in the alkyl chains and disulfide bond in the spacer was designed and synthesized. The incorporation of a cinnamoyl moiety into the alkyl chains of Gemini surfactant makes it easy to probe the conformational information of the amphiphile molecule. The UV/vis absorption spectra and steady-state fluorescence were investigated at a concentration far below the critical micelle concentration (cmc). Both blue-shift of absorption and red-shift of fluorescence emission spectra indicate the existence of intramolecular interaction between the two alkyl chains in Gemini surfactant in the singly dispersed state. Results based on the breakdown of the disulfide bond by dithiotheritol (DTT) further confirmed the conclusion. Moreover, the characteristic of intramolecular chain interaction in Gemini surfactant improves the topochemical geometrical requirements of cinnamoyl moiety and increases the local concentration of reactant in dilute solution. Utilizing the incorporation of cinnamoyl moiety into the alkyl chains of Gemini surfactant, the cinnamoyl moiety upon irradiation undergoes dimerization in dilute aqueous solution with high yield of 78%. 相似文献
14.
Iron(II) complexes of triazole derivatives having two C12 and C16 long alkyl chains, (C12trz)FeII and (C16trz)FeII, serve as novel spin-crossover materials, which display a spin-state transition in response to a phase transition. In contrast, a triazole complex with two C8 alkyl chains ((C8trz)FeII) exhibits only a poor response. EXAFS and XRD analyses of (C16trz)FeII indicate an interdigitating self-assembled structure of polynuclear iron(II) species. According to DSC, VT-IR, and VT-XRD profiles, the spin-state transition is triggered by melting of the interdigitating alkyl chains, which is likely responsible for the "lock-and-release" feature of the spin state. By virtue of the thermoreversibility of the phase transition, the spin crossover could be repeated without deterioration. 相似文献
15.
Five quinoline derivatives containing different alkyl chains (QLACn, n?=?2, 4, 6, 8, 12) were synthesized to investigate the effect of alkyl chains on their photophysical properties. The fluorescent properties of the QLACn were affected by the alkyl chains, which indicated obvious blue-shifting trend and fluorescence emission are alkyl chains length-dependent by grinding-induced spectral shifts (ΔλMFC). Longer alkyl-length revealed larger ΔλMFC. Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) measurements indicated that the transformation between microcrystalline and amorphous states upon external stimuli should be responsible for the observed reversible MFC behavior. 相似文献
16.
A series of “hairy-rod” polyimides, BBPA(n), with multiple alkyl side chains was prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-biphenyldiamine substituted in the 2,2′-positions with benzoate, which was substituted in the 3,4,5-positions with ether side chains of varying lengths. The number of the methylene units, n, in these alkyl side chains were in even numbers ranging from 8 to 18. Combining techniques of one-dimensional (1D) and 2D wide angle x-ray diffraction, 1D small angle X-ray scattering, differential scanning calorimetry experiments, it was found that this series of “hairy-rod” polyimides possess a micro-phase separation between the backbones and side chains. This led to the formation of ordered structures in two different length scales, of which both are hexagonal packing: one is attributed to the alkyl side chains on the sub-nanometer scale, and another is for the whole polymer chains on the nanometer scale. The development of the hexagonal structure on the sub-nanometer scale was critically dependent upon the lengths of the alkylside chains. Three relaxation processes were captured by dynamic mechanical analysis, i.e., segmental motion of the backbones, α the melting of the side chain crystals, β1, which exits only for the materials with longer side chains(n=18,16); and the subglass relaxation of side chains, β2- The peak relaxation temperature of the α process decreased with increasing the length of side chains, while the one of the β2 process increased. The activation energy of the α relaxation was relatively independent on the length of side chain, whereas, β2 process showed the increasing of activation energy with increasing the length of side chains. 相似文献
17.
Kikkawa Y Koyama E Tsuzuki S Fujiwara K Miyake K Tokuhisa H Kanesato M 《Langmuir : the ACS journal of surfaces and colloids》2006,22(16):6910-6914
The self-assembled monolayer of bipyridine derivative 1, which has two alkyl chains on each end, at the HOPG/1-phenyloctane interface was studied by in situ scanning tunneling microscopy (STM). The detailed mechanism of a spontaneous change in the monolayer packing pattern by Pd coordination was studied. Uncomplexed 1 existed in a bent form in the monolayer, and the alkyl chains were interdigitated, whereas Pd-complexed 1 was in a straight form and the alkyl chains were not interdigitated. An intermediate state of 1 was successfully observed during metal coordination. The structure was the bent form with noninterdigitated alkyl chains. Equilibrium intermolecular distances reported from ab initio calculations indicate that the molecular width of the central aromatic part of uncomplexed 1 (7.5 A) is substantially smaller than that of the peripheral alkyl chain part (9.2 A). The bent form was suitable for covering up the surface to maximize the packing density. However, the molecular width of the aromatic unit of Pd-complexed 1 (9.1 A) was almost identical to that of the alkyl chain unit (9.2 A). Therefore, Pd-complexed 1 took the straight form in the monolayer. The observation of surface coverage by STM suggests that the bent form increases the packing density by as much as 16% compared with that of the straight form. These results indicate that the control of molecular width can be used to design molecular templates for nanostructure formation. 相似文献
18.
Ziani K Barish JA McClements DJ Goddard JM 《Journal of colloid and interface science》2011,364(1):31-38
Polymer-hybridized liposomes (PHLs) of saturated lecithin were formed by association of poly(asparagines) grafted with alkyl chains (PAsn-g-Cn). The thermal, physical, and surface properties of the polymer-hybridized liposomes were examined with varying polymer concentration, alkyl chain length (C(8), C(12), C(18), C(22)), and degree of substitution (DS) in the polymer. The inclusion of the polymer raised the membrane fluidity of liposomes. By the incorporation of small amount of polymer, the membrane rigidity of liposomes dropped sharply and then increased close to the original level as the polymer concentrations increased in the cases of PAsn-g-C(18) and PAsn-g-C(22). Also, the membrane rigidity and stability of PHLs increased with alkyl chain length at the same polymer concentration. The surface charge of PHL associated with PAsn-g-C(22) was changed by DS of alkyl chains. The polymer bearing long alkyl chains (C(12), C(18), C(22)) formed PHLs well at low polymer concentration and the number of disk-shaped polymer-lipid mixed micelles increased with polymer concentration. The anchored polymers induced shifts in gel-to-liquid crystal transition temperature (Tc) of the vesicles and Tc varied with polymer concentration, alkyl chain length, and DS of the polymer. 相似文献
19.
The structure of micelles formed by nonionic polyoxyethylene alkyl ether nonionic surfactants, C n E m , in the room-temperature ionic liquid, ethylammonium nitrate (EAN), has been determined by small-angle neutron scattering (SANS) as a function of alkyl and ethoxy chain length, concentration, and temperature. Micelles are found to form for all alkyl chains from dodecyl through to octadecyl. Dodecyl-chained surfactants have high critical micelle concentrations, around 1 wt%, and form weakly structured micelles. Surfactants with longer alkyl chains readily form micelles in EAN. The observed micelle structure changes systematically with alkyl and ethoxy chain length, in parallel with observations in aqueous solutions. Decreasing ethoxy chain length at constant alkyl chain length leads to a sphere to rod transition. These micelles also grow into rods with increasing temperature as their cloud point is approached in EAN. 相似文献
20.
Jiale Chen Xuelong Huang Dr. Zhixiong Cao Prof. Shengjian Liu Kexin Liang Jinhai Liu Dr. Xuechen Jiao Dr. Jiaji Zhao Dr. Qingduan Li Prof. Yue-Peng Cai 《Chemphyschem》2020,21(9):908-915
For all-polymer solar cells which are composed of polymer donors and polymer acceptors, the effect of alkyl side chains on photovoltaic performance is a matter of some debate, and this effect remains difficult to forecast. In this concise contribution, we demonstrate that three alkyls namely branched alkyl 2-butyloctyl (2BO), long linear alkyl n-dodecyl (C12), and double-short linear alkyl n-hexyls (DC6) incorporated into the side chains of large bandgap polymer donor PBDT-TTz can induce considerable, of significance, and different electronic, optical, and morphological parameters. Systematic studies shed light on the critical role of the double-short linear alkyl n-hexyls (DC6) in (i) producing large ionization potential value, (ii) increasing propensity of the polymer to order along the π-stacking direction, (iii) generating polymer crystallites with more preferential “face-on” orientation, consequently, (iv) improvement of carriers transportation, (v) suppression of charge recombination, (vi) reduction of energy loss in all-polymer devices. In parallel, we unearth that the PBDT-TTz with double-short linear alkyl n-hexyls (DC6) represents the highest efficiency of 8.3 %, whereas, the other two PBDT-TTz analogues (2BO, C12) yield efficiencies of less than 3 % in optimized all-polymer solar cells. Though branched or long linear alkyl side chains (2BO, C12) have been applied to provide the solution processability of conjugated polymers, motifs bearing multiple short linear alkyl substituents (DC6) are proved critical to the development of high performing polymers. 相似文献